WO2015198779A1 - Nouveau polymère et son utilisation - Google Patents

Nouveau polymère et son utilisation Download PDF

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Publication number
WO2015198779A1
WO2015198779A1 PCT/JP2015/065118 JP2015065118W WO2015198779A1 WO 2015198779 A1 WO2015198779 A1 WO 2015198779A1 JP 2015065118 W JP2015065118 W JP 2015065118W WO 2015198779 A1 WO2015198779 A1 WO 2015198779A1
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polymer
group
resin film
formula
carbon atoms
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PCT/JP2015/065118
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English (en)
Japanese (ja)
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優 木村
寛仁 窪
武士 徳永
西村　功
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Jsr株式会社
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Priority to JP2016529202A priority Critical patent/JP6217857B2/ja
Publication of WO2015198779A1 publication Critical patent/WO2015198779A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M23/00—Constructional details, e.g. recesses, hinges
    • C12M23/20—Material Coatings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a novel polymer and photosensitive resin composition suitably used for forming a resin film containing a water-soluble resin and having a large film thickness, as well as a resin film, a patterned resin film and a method for producing the same, and
  • the present invention relates to a cell culture apparatus.
  • a spheroid is a three-dimensional cellular tissue formed by aggregation of many cells.
  • Spheroid culture is a culture method that can maintain the function of cells for a long period of time compared to conventional monolayer culture, and is closer to a living body. It is known that the survival state can be maintained over a long period of time by culturing cells in three dimensions as compared to culturing cells in two dimensions (Patent Document 1).
  • Patent Document 1 a cell culture substrate having a surface to which cells adhere relatively weakly compared to 2D culture is used, so that the problem that the formed spheroids are released into the culture solution is known.
  • Patent Document 1 a method of culturing cells in a cell holding cavity for holding cells has been disclosed (Patent Document 1).
  • a photosensitive resin composition containing a water-soluble resin which is a partition wall having a weak adhesive force with the cell tissue body in consideration of the ease of taking out the cultured cell tissue body
  • Patent Documents 2 to 3 a partition wall formed from
  • JP 2006-121991 A Japanese Patent Laid-Open No. 03-007576 JP 2014-023508 A
  • An object of the present invention is to provide a polymer, a photosensitive resin composition containing the polymer, and a resin film and a patterned resin, which can form a resin film containing a water-soluble resin and having a large film thickness.
  • An object of the present invention is to provide a membrane, a manufacturing method thereof, and a cell culture apparatus.
  • the present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by using a polymer and a photosensitive resin composition having the following configurations, and have completed the present invention.
  • the present invention includes, for example, the following [1] to [13].
  • [1] A polymer (A) having a structural unit represented by the formula (1a).
  • each R 1 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • R 2 is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms
  • R 3 is a group having a hydroxyl group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • each R 1 is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • R 2 is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms
  • R 3 is a group having a hydroxyl group
  • R 4 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • Step 1 of forming a resin film of the photosensitive resin composition according to any one of [5] to [7] on a substrate; Step 2 of selectively exposing the film; And a step 3 of developing the exposed film with an aqueous developer.
  • the polymer which can form the resin film containing a water-soluble resin and a large film thickness, the photosensitive resin composition containing this polymer, and a resin film and patterned resin A membrane, a production method thereof, and a cell culture device can be provided.
  • FIG. 1 is a 1 H NMR spectrum of the polymer obtained in Synthesis Example A1.
  • FIG. 2 is a 1 H NMR spectrum of the polymer obtained in Example A1.
  • FIG. 3 is a 1 H NMR spectrum of the polymer obtained in Example A2.
  • n is a formula number.
  • the polymer of the present invention has a structural unit represented by the formula (1ab).
  • X is —S— or —S ( ⁇ O) —
  • R 1 is each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom
  • 2 is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, preferably an alkanediyl group having 1 to 20 carbon atoms
  • R 3 is a group having a hydroxyl group
  • R 4 is A hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom.
  • polymer (A) a polymer having the above structural unit in which X is —S ( ⁇ O) — is also referred to as “polymer (A)”, and a polymer having the above structural unit in which X is —S—.
  • the polymer is also referred to as “polymer (A) precursor” or “polymer (A ′)”.
  • the polymer having both the structural unit in which X is —S ( ⁇ O) — and the structural unit in which X is —S— corresponds to the polymer (A).
  • the polymer (A) is obtained by oxidizing the precursor as described later.
  • the term “polymer of the present invention” is used to collectively refer to the polymers (A) and (A ′).
  • the polymer (A) is a water-soluble resin, it is possible to form a resin film having a cell non-adhesive property with weak adhesion to a cell tissue.
  • the “water-soluble resin” in the present invention refers to a resin having a solubility in 100 g of water at 25 ° C. and 1 bar of 0.1 g or more.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R 1 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, a decyl group, etc. are mentioned.
  • the number of carbon atoms of the alkyl group is preferably 1-15, more preferably 1-10.
  • Examples of the alkanediyl group having 1 to 20 carbon atoms in R 2 include a methylene group, a 1,2-ethanediyl group, an n-propylene group, an isopropylene group, and an isobutylene group.
  • the carbon number of the alkanediyl group is preferably 1-15, more preferably 1-10.
  • Examples of the arylene group having 6 to 20 carbon atoms in R 2 include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, , 8-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group and the like.
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms.
  • the group having a hydroxyl group in R 3 is, for example, formed by substituting at least one hydrogen atom contained in an alkyl group having usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10 carbon atoms with a hydroxyl group.
  • Examples include OH-containing groups and OH / ether-containing groups in which a part of —CH 2 — contained in the OH-containing group is replaced with an oxygen atom.
  • the number of hydroxyl groups is usually 1 or more, preferably 1 to 5, more preferably 1 to 2.
  • R 3 is preferably a monovalent group represented by the formula (g1).
  • a is an integer of 0 to 4, preferably an integer of 0 to 1.
  • the structural unit (1ab) is preferably a part of the structural unit represented by the formula (1).
  • X and R 1 to R 4 have the same meanings as the same symbols in the formula (1ab).
  • two R 1 attached to the carbon atom C 1 is a hydrogen atom, it is more preferred that all of R 1 is a hydrogen atom.
  • the content of the structural unit (1) in which X is —S ( ⁇ O) — is usually 20 mol% or more, preferably 20 to 20 mol per 100 mol% of all the structural units constituting the polymer (A) of the present invention. 90 mol%, more preferably 30 to 80 mol%.
  • the content of the structural unit (1) in which X is —S— is usually 20 mol% or more, preferably 20 to 90 mol% in 100 mol% of all the structural units constituting the polymer (A ′) of the present invention. More preferably, it is 30 to 80 mol%.
  • the structural unit indicates a structure derived from a monomer (for example, a conjugated diene compound). The content of each structural unit can be measured by NMR analysis.
  • the polymer of the present invention may further have a structural unit represented by the formula (2), and from the structural unit represented by the formula (3) and the structural unit represented by the formula (4). You may have further at least 1 sort chosen.
  • X and R 1 to R 4 have the same meanings as the same symbols in the formula (1ab).
  • the cis-trans isomer of the double bond is not particularly limited. Incidentally, it is preferable that two R 1 attached to the carbon atom C 1 is a hydrogen atom, it is more preferred that all of R 1 is a hydrogen atom.
  • the total content of the structural unit (1) and the structural unit (2) in which X is —S ( ⁇ O) — is usually 20 mol in 100 mol% of all structural units constituting the polymer (A) of the present invention. % Or more, preferably 20 to 95 mol%, more preferably 30 to 90 mol%.
  • the content of the structural unit (1) and the structural unit (2) in which X is —S— is usually 20 mol% or more, preferably 100 mol% or more in all the structural units constituting the polymer (A ′) of the present invention. Is 20 to 95 mol%, more preferably 30 to 90 mol%.
  • the content of the structural unit (3) is usually 80 mol% or less, preferably 5 to 80 mol%, more preferably 100 mol% of all the structural units constituting the polymer (A) or (A ′) of the present invention. Is from 10 to 70 mol%.
  • the content of the structural unit (4) in which X is —S ( ⁇ O) — is usually 10 mol% or less in 100 mol% of all the structural units constituting the polymer (A) of the present invention.
  • the content of the structural unit (4) in which X is —S— is usually 10 mol% or less in 100 mol% of all the structural units constituting the polymer (A ′) of the present invention.
  • the weight average molecular weight (Mw) measured by the gel permeation chromatography method of the polymer of the present invention is usually 1,000 to 100,000, preferably 2,000 to 50,000, more preferably in terms of polystyrene. 3,000 to 30,000. Further, the molecular weight distribution of the polymer of the present invention represented by weight average molecular weight (Mw) / number average molecular weight (Mn) is usually 1 to 5, preferably 1.1 to 3, more preferably 1.2 to 2. It is.
  • Mw is in the above range
  • a resin film having a higher resolution and a larger film thickness can be formed. It is preferable in terms of resolution that Mw / Mn is in the above range.
  • the details of the measuring method of Mw and Mn are as described in the examples.
  • the polymer (A) of the present invention includes, for example, a step A1 of obtaining an epoxidized polymer by epoxidizing a carbon-carbon double bond contained in a conjugated diene polymer, and an epoxy ring contained in the epoxidized polymer.
  • ring-opening addition of a compound represented by R 3 —R 2 —SH (R 2 and R 3 have the same meanings as R 2 and R 3 in the formula (1ab), respectively) It can be synthesized by a production method having Step A2 for obtaining a containing polymer and Step A3 for converting a sulfide group contained in the sulfide group-containing polymer into a sulfinyl group using an oxidizing agent.
  • Step A1 is a step of obtaining an epoxidized polymer by epoxidizing the carbon-carbon double bond contained in the conjugated diene polymer.
  • the carbon-carbon double bond contained in the conjugated diene polymer having the structural unit represented by the formula (a1) is epoxidized, and the epoxidized polymer having the structural unit represented by the formula (a2) Is obtained.
  • R 1 has the same meaning as the same symbol in formula (1ab).
  • the cis-trans isomer of the double bond is not particularly limited.
  • conjugated diene compound constituting the conjugated diene polymer examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, and 1,3- Examples include pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, and 4,5-diethyl-1,3-octadiene. Of these, 1,3-butadiene and isoprene are preferred.
  • a conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.
  • polybutadiene and polyisoprene are preferable.
  • the vinyl bond content in the conjugated diene polymer is usually 80 mol% or less, preferably 5 to 80 mol%, more preferably 10 to 70 mol%.
  • the vinyl bond content is a conjugated diene compound that is incorporated in a conjugated diene polymer in a 1,2-bond, 3,4-bond, or 1,4-bond bond mode. This is the total ratio (based on mol%) of compounds incorporated by 1,2-bonds and 3,4-bonds.
  • the vinyl bond content can be measured by the Hampton method by infrared spectroscopic analysis.
  • Step A1 can be performed, for example, by epoxidizing the carbon-carbon double bond derived from the conjugated diene compound contained in the conjugated diene polymer with an epoxidizing agent in an organic solvent.
  • an epoxidation catalyst can also be used.
  • Examples of the epoxidizing agent include hydrogen peroxide; organic peracids such as peracetic acid, perbenzoic acid, performic acid, and trifluoroperacetic acid. Among these, hydrogen peroxide is preferable.
  • Examples of the epoxidation catalyst include formic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid Vaccenoic acid, linoleic acid, (9,12,15) -linolenic acid, (6,9,12) -linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid, 8,11-icosadienoic acid, 5 , 8,11-icosatrienoic acid, arachidonic acid, behenic acid,
  • organic solvents examples include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cycloheptane, benzene, naphthalene, toluene, and xylene.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • the reaction temperature in step A1 may be appropriately selected below the boiling point of the solvent, but is usually 0 to 200 ° C., preferably 40 to 150 ° C.
  • the reaction time in step A1 is usually 0.5 to 30 hours, preferably 1 to 10 hours.
  • the amount of epoxidizing agent and epoxidation catalyst used is not particularly limited. An appropriate amount can be used depending on conditions such as the reactivity of the epoxidizing agent, the performance of the epoxidation catalyst, the desired epoxidation rate, the number of carbon-carbon double bonds contained in the conjugated diene polymer.
  • the epoxidation rate of the epoxidized polymer is usually 10 to 100%, preferably 30 to 90%, more preferably 40 to 80%.
  • Epoxidation rate is [number of double bonds epoxidized among all carbon-carbon double bonds contained in conjugated diene polymer / number of all carbon-carbon double bonds contained in conjugated diene polymer before epoxidation] ⁇ 100 (%).
  • the epoxidation rate can be calculated by 1 H NMR.
  • Step A2 is a step of obtaining a sulfide group-containing polymer by ring-opening addition of a compound (sulfiding agent) represented by R 3 —R 2 —SH to the epoxy ring contained in the epoxidized polymer. . If necessary, the hydroxyl group after the epoxy ring is opened is alkoxylated. In this step, the structural unit represented by the formula (a2) is converted into the structural unit represented by the formula (a3) to obtain the precursor of the polymer (A) of the present invention.
  • a compound (sulfiding agent) represented by R 3 —R 2 —SH
  • R 1 to R 4 are respectively synonymous with the same symbols in formula (1ab).
  • R 2 and R 3 are as defined the same symbols in each formula (1ab). Specific examples include thioglycerol and mercaptoethanol.
  • the sulfiding agent may be used alone or in combination of two or more.
  • the amount of the sulfidizing agent to be used is generally 0.5 to 20 mol, preferably 1 to 10 mol, per 1 mol of structural unit (a2).
  • Step A2 is preferably performed in the presence of a catalyst.
  • the catalyst include basic catalysts such as lithium hydroxide, triethylamine and N, N-dimethyl-4-aminopyridine.
  • a catalyst may be used individually by 1 type and may use 2 or more types together.
  • the amount of the catalyst to be used is generally 0.01-30 mol, preferably 0.1-10 mol, per 1 mol of structural unit (a2).
  • Step A2 is preferably performed in the presence of an organic solvent.
  • the organic solvent include alcohol solvents such as methanol and ethanol, amide solvents such as dimethylformamide and dimethylacetamide, sulfoxide solvents such as dimethyl sulfoxide, ester solvents such as ethyl acetate, butyl acetate and ⁇ -butyrolactone, toluene, benzene and the like.
  • an aromatic solvent such as tetrahydrofuran, dioxane, diethyl ether and the like.
  • An organic solvent may be used individually by 1 type, and may use 2 or more types together.
  • the reaction temperature in step A2 may be appropriately selected below the boiling point of the solvent, but is usually 30 to 150 ° C., preferably 40 to 100 ° C.
  • the reaction time in step A2 is usually 1 to 20 hours, preferably 2 to 10 hours.
  • the alkoxylation of the hydroxyl group formed by opening the epoxy ring can be performed by a known method. For example, it can be carried out according to the method described in JP-A-56-104831 or JP-A-2005-305280.
  • the alkoxylation of the hydroxyl group may be performed after sulfinylation.
  • Step A3 is a step of converting a sulfide group contained in the sulfide group-containing polymer into a sulfinyl group using an oxidizing agent.
  • the structural unit represented by the formula (a3) is converted into the structural unit represented by the formula (a4), and the polymer (A) of the present invention is obtained.
  • R 1 to R 4 are respectively synonymous with the same symbols in formula (1ab).
  • the oxidizing agent examples include organic oxidizing agents such as peracetic acid, perbenzoic acid, and metachloroperbenzoic acid, and inorganic oxidizing agents such as hydrogen peroxide, chromic acid, and permanganate.
  • An oxidizing agent may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the oxidizing agent to be used is generally 1 to 10 mol, preferably 2 to 5 mol, per 1 mol of structural unit (a3).
  • An oxidizing agent may be used individually by 1 type, and may use 2 or more types together.
  • Process A3 is preferably performed in the presence of a solvent.
  • the solvent include water; alcohol solvents such as methanol and ethanol; amide solvents such as dimethylformamide and dimethylacetamide. Among these, water and alcohol solvents are preferable.
  • a solvent may be used individually by 1 type and may use 2 or more types together.
  • the reaction temperature in step A3 may be appropriately selected below the boiling point of the solvent, but is usually 23 to 100 ° C., preferably 30 to 70 ° C.
  • the reaction time in step A3 is usually 0.5 to 30 hours, preferably 1 to 10 hours.
  • isolation of each reaction product is carried out as usual by filtration, washing, drying, recrystallization, reprecipitation, dialysis, centrifugation, extraction with various solvents, neutralization, chromatography, etc.
  • the means may be combined appropriately.
  • the photosensitive resin composition of this invention contains the polymer (A) mentioned above, a photoresponsive compound (B), and a crosslinking agent (C).
  • the photosensitive resin composition of the present invention is also referred to as “the composition of the present invention”. Since the composition of this invention contains a polymer (A), it can form the resin film which has a large film thickness and hydrophilic property.
  • the viscosity of the composition of the present invention is usually 0.1 to 100 cP, preferably 0.5 to 50 cP, more preferably 1 to 10 cP.
  • the viscosity is a value measured by a method based on JIS Z8803.
  • the content of the polymer (A) is usually 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass in 100% by mass of the composition of the present invention.
  • the content of the polymer (A) is within the above range, a composition capable of forming a resin film having a large film thickness and high resolution can be obtained.
  • coated can be obtained.
  • the photosensitive resin composition of the present invention contains a photoresponsive compound (B).
  • Examples of the photoresponsive compound (B) include a photoacid generator and a photoradical polymerization initiator.
  • the photoacid generator is a compound that generates an acid by a treatment including light irradiation.
  • an acid is generated in the exposed part based on the acid generator, and the solubility of the exposed part in the aqueous developer is changed based on the action of this acid. To do.
  • the composition of the present invention may be either a negative type or a positive type.
  • the kind of photoresponsive compound (B) can be suitably selected according to a negative composition or a positive composition. Among these, from the viewpoint of the mechanical strength of the resin film, a negative composition is preferable.
  • the photoacid generator examples include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and compounds having a quinonediazide group.
  • the compound having a quinonediazide group is also referred to as “quinonediazide compound (B2)”, and the other exemplified photoacid generators are also referred to as “acid generator (B1)”.
  • the acid generator (B1) is a compound that generates an acid when irradiated with light.
  • the generated acid acts on the crosslinking agent (C) and the like to form a crosslinked structure.
  • it becomes a hardly soluble film.
  • a negative pattern is formed by utilizing the fact that the film changes from an easily soluble state to an insoluble state in an aqueous developer by light irradiation.
  • the quinonediazide compound (B2) is a compound in which a quinonediazide group is decomposed to generate a carboxyl group by light irradiation and contact treatment with water.
  • the resin film obtained from the composition containing the quinonediazide compound (B2) is a film that is hardly soluble in an aqueous developer.
  • a positive pattern is formed by utilizing the fact that the film changes from a hardly soluble state to an easily soluble state in an aqueous developer by light irradiation.
  • the acid generator (B1) is at least one selected from, for example, an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.
  • onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
  • preferred onium salts include iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; L-methanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenylpheny
  • halogen-containing compound examples include a haloalkyl group-containing heterocyclic compound and a haloalkyl group-containing hydrocarbon compound.
  • preferred halogen-containing compounds include phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl S-triazine derivatives such as bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine; 1 , 10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.
  • sulfone compounds include ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds, and ⁇ -diazo compounds of these compounds.
  • Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.
  • sulfonic acid compounds examples include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
  • Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.
  • sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy).
  • sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy).
  • Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (trifluoromethylsulfonyloxy) naphthylimide.
  • diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.
  • the acid generator (B1) may be used alone or in combination of two or more.
  • the content of the acid generator (B1) is preferably 100 parts by mass of the polymer (A).
  • the amount is 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • the content of the acid generator (B1) is equal to or higher than the lower limit, the exposed area is sufficiently cured and the heat resistance is easily improved.
  • the content of the acid generator (B1) is not more than the above upper limit value, a patterned resin film having a high resolution is easily obtained without lowering the transparency to exposure light.
  • quinonediazide compound (B2) examples include a naphthoquinonediazide compound, specifically, a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphtho Examples include ester compounds with quinonediazide-5-sulfonic acid.
  • Examples of the quinonediazide compound (B2) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1 A compound selected from bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphen
  • a quinonediazide compound (B2) may be used by 1 type, and may use 2 or more types together.
  • the content of the quinonediazide compound (B2) is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polymer (A). 50 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 30 parts by mass.
  • the content of the quinonediazide compound (B2) is equal to or higher than the lower limit, the remaining film ratio in the unexposed area is improved and an image faithful to the mask pattern is easily obtained.
  • the content of the quinonediazide compound (B2) is less than or equal to the above upper limit value, a resin film excellent in pattern shape is easily obtained and foaming during film formation tends to be prevented.
  • the composition of the present invention contains a crosslinking agent (C).
  • the crosslinking agent (C) is, for example, a compound that undergoes a crosslinking reaction by the action of an acid; a compound that is polymerized by heat or radical, such as a (meth) acrylate compound.
  • a compound that proceeds with a crosslinking reaction by the action of an acid is preferable.
  • crosslinking agent (C) examples include a crosslinking agent (C1) having at least two groups represented by —CH 2 OR and other crosslinking agents (C2).
  • R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acetyl group.
  • the (C1) is also referred to as “active methylene group-containing crosslinking agent (C1)”.
  • a crosslinking agent (C1) is preferable from the viewpoint that a high-thickness resin film can be formed.
  • the content of the crosslinking agent (C) is usually 1 to 50 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 20 parts per 100 parts by weight of the polymer (A). Part by mass.
  • the content of the crosslinking agent (C) is in the above range, a composition excellent in sensitivity and resolution tends to be obtained.
  • the active methylene group-containing crosslinking agent (C1) is a crosslinking agent having at least two groups represented by —CH 2 OR.
  • R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • crosslinking agent (C1) examples include a compound having two or more groups represented by the formula (C1-1) and a compound having two or more groups represented by the formula (C1-2).
  • m is 1 or 2
  • n is 0 or 1
  • m + n is 2
  • R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An acetyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond.
  • Examples of the crosslinking agent (C1) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; active methylol groups in the nitrogen compounds (CH bonded to N atom) 2 OH group) or all of a part thereof are alkyl etherified or acetoxylated.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be the same as or different from each other.
  • the active methylol group which is not alkyletherified or acetoxylated may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
  • crosslinking agent (C1) examples include crosslinking agents described in JP-A-6-180501, JP-A-2006-178059, and JP-A-2012-226297.
  • melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, tetrabutoxy Glycoluril-based crosslinking agents such as methylglycoluril; 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [ 5.5] Undecane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetrao
  • crosslinking agent (C1) examples include a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, and an acetoxymethyl group-containing phenol compound.
  • Specific examples include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and compounds represented by the following formulae. It is done.
  • a crosslinking agent (C1) may be used by 1 type, and may use 2 or more types together.
  • cross-linking agent (C2) examples include an oxirane ring-containing compound, an oxetane ring-containing compound, an isocyanate group-containing compound (including a blocked one), an oxazoline ring-containing compound, and an aldehyde group-containing phenol compound. .
  • the other crosslinking agent (C2) may be used alone or in combination of two or more.
  • the composition of the present invention preferably contains a solvent (D).
  • a solvent D
  • the handleability of the composition can be improved, and the viscosity and storage stability can be adjusted.
  • the solvent (D) for example, water or a mixed solvent containing water is preferable.
  • the solvent other than water constituting the mixed solvent include organic solvents that can be uniformly mixed with water, for example, alcohols such as methanol, ethanol, n-butanol, and ethyl lactate, and alkylene glycols such as propylene glycol monomethyl ether. .
  • the mixed solvent usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more is water.
  • a solvent (D) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the solvent (D) is such that the solid content concentration in the composition usually exceeds 10% by mass and is 70% by mass or less, preferably 15% by mass. Is more than 60% by mass, more preferably more than 20% by mass and 55% by mass or less.
  • the solid content usually means all components other than the solvent (D) contained in the composition.
  • additives In the composition of the present invention, other additives such as adhesion assistant, acid diffusion controller, crosslinked fine particles, leveling agent, surfactant, sensitizer, inorganic filler, quencher, etc. It can be contained as long as the characteristics are not impaired.
  • the composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.
  • the resin film of the present invention contains the polymer (A) described above.
  • the resin film containing the polymer (A) can be formed, for example, according to Step 1 described below, using the above-described photosensitive resin composition of the present invention.
  • the thickness of the resin film is usually 1 to 200 ⁇ m, preferably 3 to 100 ⁇ m, more preferably 5 to 50 ⁇ m.
  • the patterned resin film of the present invention contains the polymer (A) described above, and is formed, for example, from the photosensitive resin composition of the present invention.
  • a hydrophilic resin film having a large film thickness can be formed.
  • a patterned resin film with high resolution can be formed.
  • Step 1 for forming a resin film of the photosensitive resin composition of the present invention on a substrate
  • Step 2 for selectively exposing the film, and development of the exposed film with an aqueous developer.
  • a step 3 of forming a patterned resin film This manufacturing example may further include a step 4 of heat-treating the patterned resin film.
  • step 1 the photosensitive resin composition of the present invention is applied onto a substrate and dried to form a resin film.
  • drying conditions for example, heating is performed at 50 to 90 ° C. for 1 to 30 minutes using an oven or a hot plate.
  • the thickness of the resin film is usually 1 to 200 ⁇ m, preferably 3 to 100 ⁇ m, more preferably 5 to 50 ⁇ m. If the film thickness is insufficient, the resin film may be formed by coating twice.
  • the substrate for example, polystyrene, polycarbonate, polyacetal, triacetyl cellulose, polyamide, polyimide, polyethylene, polypropylene, vinyl chloride, vinylidene chloride, polyphenylene sulfide, polyethersulfone, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyacrylate,
  • a resin substrate made of at least one resin selected from polymethacrylate and cellulose; a substrate made of a material such as glass, ceramic, and stainless steel. It may be a resin substrate made of a biodegradable polymer such as polylactic acid, polyglycolic acid, and polycaprolactan.
  • a known cell culture substrate described in JP-A-2002-335949 can also be used.
  • Examples of the coating method of the composition include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.
  • step 2 the film is exposed through a desired mask pattern using, for example, a contact aligner, a stepper, or a scanner.
  • exposure light include ultraviolet light and visible light, and light with a wavelength of 200 to 500 nm (eg, i-line (365 nm)) is usually used.
  • the exposure dose of exposure light varies depending on the type and content of each component in the photosensitive resin composition, the thickness of the resin film, and the like. 000 mJ / cm 2 .
  • PEB processing In the case of using a negative photosensitive resin composition, it is preferable to perform a heat treatment after exposure in order to further promote the crosslinking reaction.
  • this processing is also referred to as “PEB processing”.
  • the PEB condition varies depending on the type and content of each component in the photosensitive resin composition and the thickness of the resin film, but is usually 50 to 90 ° C. and about 1 to 60 minutes.
  • step 3 the exposed film is developed with an aqueous developer, and a non-exposed portion is removed in the case of a negative type, and an exposed portion is removed in the case of a positive type, thereby forming a desired pattern on the substrate.
  • a resin film is formed.
  • aqueous developer for example, water or a mixed solvent containing water is preferable.
  • a mixed solvent the mixed solvent described in the column of the solvent (D) is mentioned.
  • the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method.
  • the development conditions are usually about 20 to 40 ° C. for about 1 to 10 minutes.
  • the patterned resin film is further cured by heating.
  • the heating conditions are not particularly limited, but for example, the heating is performed at a temperature of 100 to 300 ° C. for about 30 minutes to 10 hours depending on the use of the patterned resin film. In order to sufficiently advance the curing or to prevent the deformation of the pattern shape, heating can be performed in multiple stages.
  • the cell culture device of the present invention has the patterned resin film described above.
  • the apparatus preferably includes a cell culture substrate and the patterned resin film described above formed on the substrate.
  • the patterned resin film possessed by the cell culture device of the present invention is a resin film formed from the photosensitive resin composition of the present invention for retaining cells and cell tissues formed from these cells, particularly spheroids. It has a structure in which one or a plurality of holes are formed.
  • the patterned resin film is a partition wall that forms a hole.
  • the hole is formed through the resin film.
  • the bottom surface of the hole is constituted by the surface of the cell culture substrate, and the side surface of the hole is constituted by a resin film.
  • the surface of the cell culture substrate preferably has cell adhesion from the viewpoint of cell retention.
  • the patterned resin film preferably has cell non-adhesiveness in consideration of the ease of removing the cell tissue from the pores after culturing. Since the photosensitive resin composition of the present invention contains the polymer (A) which is a water-soluble resin, a patterned resin film having the above properties can be formed.
  • the shape of the bottom surface of the hole is not particularly limited, and examples thereof include a circular shape, an elliptical shape, and a polygonal shape.
  • the area of the bottom of the pore is appropriately determined depending on the size and type of cells, but is usually 1,000 to 40,000 ⁇ m 2 , preferably 5,000 to 20,000 ⁇ m 2 .
  • the patterned resin film in which holes are formed in the resin film can be formed, for example, according to the above-described method for producing a patterned resin film.
  • a cell culture substrate is used as the substrate to which the photosensitive resin composition is applied.
  • the bottom surface of the hole is preferably a surface having cell adhesiveness from the viewpoint of holding cells and forming a cell tissue body.
  • Cell adhesive surfaces include, for example, surfaces into which charged functional groups such as carboxyl groups and amino groups have been introduced, surfaces into which cell adhesive peptides such as arginine, glycine, and aspartic acid sequences have been introduced. It is the surface where the polymer which it has was fixed.
  • the functional group having an electric charge can be introduced by treating the substrate surface with radiation such as plasma.
  • the polymer having cell adhesion include, for example, synthetic polymers having a charge such as polyacrylic acid, polyvinyl sulfate, polystyrene sulfonic acid, polyallylamine, chondroitin sulfate, dermatan sulfate, dextran sulfate, keratan sulfate, heparan sulfate, Examples thereof include polysaccharides having a charge such as hyaluronic acid and chitin, cell adhesive proteins such as collagen, gelatin, fibronectin, hydronectin and laminin, and synthetic polymers on which cell adhesive proteins and cell adhesive peptides are immobilized.
  • a cell culture substrate having a cell adhesive surface can be used. Further, after the patterned resin film is formed on the cell culture substrate, the exposed surface of the substrate (bottom surface of the hole) may be subjected to radiation treatment or a cell-adhesive polymer may be immobilized.
  • the substrate surface that is the bottom surface of the hole may have an uneven structure.
  • the adhesion of the cell tissue body to the bottom surface can be improved.
  • Examples of the shape in the planar direction of the convex portion or concave portion in the concavo-convex structure include a circular shape, an elliptical shape, and a polygonal shape.
  • the depth of the hole is determined by the thickness of the patterned resin film, and is usually 1 to 200 ⁇ m, preferably 3 to 100 ⁇ m, and more preferably 5 to 50 ⁇ m. If it is this range, a cell and a cell tissue body can be favorably hold
  • the cells are cultured in the pores of the patterned resin film to form cell tissues, particularly spheroids.
  • a culture solution containing cells is put into the hole, and cells seeded on the bottom surface of the hole form a cell tissue body that is three-dimensionally bonded on the surface of the cell culture substrate that is the bottom surface.
  • the cell tissue is cultured for a long period of time while being stably held in the hole formed by the partition wall while adhering to the bottom surface of the hole without floating in the culture solution.
  • the type of animal species and organs / tissues is not particularly limited as long as the cells form a bond between cells.
  • primary cells collected from livers, pancreas, kidneys, nerves, skin, ES cells (Embryonic Stem cell), established cell lines, or these derived from animals such as humans, pigs, dogs, rats, mice, etc. And cells subjected to genetic manipulation.
  • a cell may be used individually by 1 type and may use 2 or more types together.
  • As the culture solution an aqueous solution containing necessary salts and / or nutrient components at an appropriate concentration can be used so that the survival state and function of the cells can be maintained.
  • Method for measuring physical properties [1] Method for measuring Mw, Mn and Mw / Mn of polymer
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer are: The measurement was performed by gel permeation chromatography under the following conditions. Column: Tosoh column “TSKgel ⁇ M” and “TSKgel ⁇ 2500” connected in series. Solvent: N-methyl-2-pyrrolidone with lithium bromide and phosphoric acid added. Temperature: 40 ° C. ⁇ Detection method: Refractive index method ⁇ Standard material: Polystyrene ⁇ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8020-GPC”
  • the polymer (A1) is a polymer in which a part of unsaturated groups of polybutadiene is epoxidized, and the epoxidation rate [(number of epoxidized unsaturated groups / polybutadiene before epoxidation is included) Number of unsaturated groups) ⁇ 100 (%)] was 60%.
  • the 1 H NMR spectrum of the polymer (A1) is shown in FIG. Moreover, Mn was 5400, Mw was 9500, and Mw / Mn was 1.76.
  • Example A1 Synthesis of polymer (A2)
  • polymer (A2) In a 100 ml flask, 5.2 g of the above polymer (A1), 4.4 g of ⁇ -thioglycerol, 0.85 g of lithium hydroxide monohydrate, methanol (MeOH). 6.6 ml and tetrahydrofuran (THF) 5.8 ml were added and heated and stirred at 60 ° C. for 2 hours. Then, it cooled to 23 degreeC and reprecipitated with water. The precipitate was vacuum dried at 60 ° C. to obtain a polymer (A2). From 1 H NMR, it was found that the polymer (A2) had a thioether structure. The 1 H NMR spectrum of the polymer (A2) is shown in FIG.
  • Example A2 Synthesis of polymer (A3) To a 100 ml flask, 5.0 g of the above polymer (A2), 4.6 g of 31% by mass hydrogen peroxide, and 25.3 ml of methanol (MeOH) were added. The mixture was stirred with heating at ° C for 2 hours. Then, it cooled to 23 degreeC and reprecipitated with isopropanol. The precipitate was vacuum dried at 60 ° C. to obtain a white solid polymer (A3). From 1 H NMR, it was found that the polymer (A3) had a sulfinyl group. The 1 H NMR spectrum of the polymer (A3) is shown in FIG.
  • Example 1C On the glass substrate, the photosensitive resin composition prepared in Example 1B was applied by spin coating, heated at 70 ° C. for 20 minutes using a hot plate, and the film thickness was 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, and 20 ⁇ m. A resin film was formed. Next, using an aligner (manufactured by Suss Microtec, device name “MA-100”), UV light from a high-pressure mercury lamp is passed through a pattern mask so that the exposure amount at a wavelength of 365 nm is 1,000 mJ / cm 2. The film was irradiated. The exposed resin film was heated at 70 ° C.
  • an aligner manufactured by Suss Microtec, device name “MA-100”
  • Example 1B A patterned resin film having a hole pattern with a rectangular cross section was formed. It was revealed that the photosensitive resin composition prepared in Example 1B can form a good patterned resin film up to a thickness of 20 ⁇ m.
  • Comparative Example 1C was performed in the same manner as Example 1C, except that a commercially available photosensitive resin composition (trade name “Biosurfine-AWP”, manufactured by Toyo Gosei Co., Ltd.) was used as the photosensitive resin composition.
  • a commercially available photosensitive resin composition (trade name “Biosurfine-AWP”, manufactured by Toyo Gosei Co., Ltd.) was used as the photosensitive resin composition.
  • a commercially available photosensitive resin composition can form a good patterned resin film only up to a thickness of 2 ⁇ m.

Abstract

Le problème abordé par la présente invention est de pourvoir à un polymère qui permet de former un film résineux qui contient une résine soluble dans l'eau et est épais et à une composition de résine photosensible le contenant. La solution selon l'invention porte sur un polymère (A) ayant un motif structural représenté par la formule (1a). [Dans la formule (1a), les fractions R1 sont chacune indépendamment un atome d'hydrogène ou un groupe alkyle C1-20 ; R2 est un groupe alcanediyle C1-20 ou un groupe arylène C6-20 ; R3 est un groupe ayant un groupe hydroxy ; et R4 est un atome d'hydrogène ou un groupe alkyle C1-20].
PCT/JP2015/065118 2014-06-24 2015-05-26 Nouveau polymère et son utilisation WO2015198779A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017209301A1 (fr) * 2016-06-03 2017-12-07 Jsr株式会社 Plaque de puits, feuille de plaque de puits et procédé de culture
JP2018004939A (ja) * 2016-07-01 2018-01-11 Jsr株式会社 感光性樹脂組成物、細胞培養基板およびその製造方法、ならびに細胞培養基材用処理剤

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689450A (en) * 1970-10-29 1972-09-05 Phillips Petroleum Co Method of preparing sealants from polybutadiene and mercapto hydroxy compounds
JPS5365387A (en) * 1976-11-23 1978-06-10 Bayer Ag Process for producing improved polybutadiene
JPS5744602A (en) * 1980-07-05 1982-03-13 Bayer Ag Novel bonding agent, synthesis thereof and use as electrodeposition paint
JPS5944045A (ja) * 1982-09-06 1984-03-12 Nippon Soda Co Ltd メルカプト変性ポリブタジエン系感光性樹脂
JPH03205452A (ja) * 1989-10-23 1991-09-06 Mitsubishi Rayon Co Ltd ポリアリーレンサルファイド樹脂組成物
JPH0873521A (ja) * 1994-09-09 1996-03-19 Daicel Chem Ind Ltd 粘接着剤用ブロック共重合体
JPH10120850A (ja) * 1996-10-18 1998-05-12 Jsr Corp エポキシ変性エチレン−α−オレフィン−非共役ジエン共重合ゴム組成物
JP2001253911A (ja) * 2000-03-09 2001-09-18 Nippon Mitsubishi Oil Corp エポキシ基およびアルコキシシリル基を有するポリブタジエン誘導体
JP2011079978A (ja) * 2009-10-07 2011-04-21 Ube Industries Ltd 変性ジエン系ゴムおよびゴム組成物
EP2530094A1 (fr) * 2011-05-31 2012-12-05 TSRC Corporation Procédé de production de polymère de type époxyde

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689450A (en) * 1970-10-29 1972-09-05 Phillips Petroleum Co Method of preparing sealants from polybutadiene and mercapto hydroxy compounds
JPS5365387A (en) * 1976-11-23 1978-06-10 Bayer Ag Process for producing improved polybutadiene
JPS5744602A (en) * 1980-07-05 1982-03-13 Bayer Ag Novel bonding agent, synthesis thereof and use as electrodeposition paint
JPS5944045A (ja) * 1982-09-06 1984-03-12 Nippon Soda Co Ltd メルカプト変性ポリブタジエン系感光性樹脂
JPH03205452A (ja) * 1989-10-23 1991-09-06 Mitsubishi Rayon Co Ltd ポリアリーレンサルファイド樹脂組成物
JPH0873521A (ja) * 1994-09-09 1996-03-19 Daicel Chem Ind Ltd 粘接着剤用ブロック共重合体
JPH10120850A (ja) * 1996-10-18 1998-05-12 Jsr Corp エポキシ変性エチレン−α−オレフィン−非共役ジエン共重合ゴム組成物
JP2001253911A (ja) * 2000-03-09 2001-09-18 Nippon Mitsubishi Oil Corp エポキシ基およびアルコキシシリル基を有するポリブタジエン誘導体
JP2011079978A (ja) * 2009-10-07 2011-04-21 Ube Industries Ltd 変性ジエン系ゴムおよびゴム組成物
EP2530094A1 (fr) * 2011-05-31 2012-12-05 TSRC Corporation Procédé de production de polymère de type époxyde

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017209301A1 (fr) * 2016-06-03 2017-12-07 Jsr株式会社 Plaque de puits, feuille de plaque de puits et procédé de culture
JP2018004939A (ja) * 2016-07-01 2018-01-11 Jsr株式会社 感光性樹脂組成物、細胞培養基板およびその製造方法、ならびに細胞培養基材用処理剤

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